Lecture 10 Proton

Balance, Graphical
Solutions & Ionization
Proton balance equation
balance on H+)
Fractions
for (mass
Multiprotic
Graphical solutions for multiprotic systems
Systems
Plot species concentration (pC) versus Master Variable (pH)

Diprotic

[H+]: pH = pH
[OH-]: pOH = pKW - pH

[H2B] = BT* 0

[HB-] = BT* 1
[B2-] = BT* 2

Start with System Definition

System: Closed
Components: HA & H2O

Species: HA, A-, H2O, OH-, H+

Equilibria:

H2O = H+ + OH-

Kw = [H+][OH-] = 10-14
HA = H+ + AKA = [H+][A-]/[HA] = 10-6

Mass Balance: AT = [HA] + [A-] = 10-3 M

Charge Balance: [A-] + [OH-] = [H+]

Summary of steps

Plot line for [H+]: pH = pH

Plot line for [OH-]: pOH = pKW -pH

Plot AT: horizontal line at pC = pAT

Plot system point: pH = pKA on pAT line

Plot AT
System
point
AT

Lines for the acid species

Acid species [HA]: Combine mass balance and mass

action to get

H A
[ HA]
K H
In log form
log[ HA] log H log A log K H
T

At low pH (pH << pKA)

log[ HA] log AT

At high pH (pH >> pKA)

log[ HA] log H log AT log K A

pH dependence of pHA

HA

Lines for the acid species

Conjugate base [A-]: Combine mass balance and mass

action to get
K A AT

[A ]
KA H
In log form

log[ A ] log K A log AT log K A H

At low pH (pH << pKA)

log[ A ] log K A log AT log H

At high pH (pH >> pKA)

log[ A ] log AT

Including dependence of [A-]

with pH

Complete system
Intercept
~ 0.3 log
below AT

System with 10-3 M Benzoic

Acid

System with 10-3 M Benzoic

Acid

What is the equilibrium pH for a

solution comprised of AT M of the salt

Closed
ofSystem:
the conjugate
base, NaA?

Components: Na+, HA & H2O

Species: HA, A-, H2O, OH-, H+

Equilibria:

H2O = H+ + OH-

Kw = [H+][OH-] = 10-14
HA = H+ + AKA = [H+][A-]/[HA] = 10-pKa

Mass Balance: AT = [HA] + [A-]

NaT = [Na+] = AT

Charge Balance: [A-] + [OH-] = [H+] + [Na+]

Proton Balance equation: [HA] + [H +] = [OH-]

Monoprotic Weak Acid NaAcetate (salt of the conjugate

base)

What is the equilibrium pH for a

solution comprised of AT M of the salt

Closed
ofSystem:
the conjugate
base, NaA?

Components: Na+, HA & H2O

Species: HA, A-, H2O, OH-, H+

Equilibria:

H2O = H+ + OH-

Kw = [H+][OH-] = 10-14
HA = H+ + AKA = [H+][A-]/[HA] = 10-pKa

Mass Balance: AT = [HA] + [A-]

NaT = [Na+] = AT

Charge Balance: [A-] + [OH-] = [H+] + [Na+]

Proton Balance equation: [HA] + [H +] = [OH-]

Monoprotic Weak Acid NaAcetate (salt of the conjugate

base)

Monoprotic Weak Acid - NaCN

(salt of the conjugate base)

What is the equilibrium pH for a

solution comprised of BT M of a generic
System: Closed
acid diprotic acid H2B?

Components: H2B & H2O

Species: H2B, HB-,B2- H2O, OH-, H+

Equilibria:

H2O = H+ + OH-

Kw = [H+][OH-] = 10-14
H2B = H+ + HBKA1 = [H+][HB-]/[H2B] = 10-pKa1
HB- = H+ + B2KA2 = [H+][B2-]/[HB-] = 10-pKa2

Mass Balance: BT = [H2B] + [HB-] +[B2-]

Charge Balance ( = PBC): 2[B2-] + [HB-] + [OH-] = [H+]

Diprotic Acid - Carbonate

System
system
points
CT

What is the equilibrium pH for a

solution comprised of BT M of the salt
System: Closed
of the conjugate base of H2B?

Components: Na+, H2B & H2O

Species: H2B, HB-,B2- H2O, OH-, H+

Equilibria:
H2O = H+ + OH-

Kw = [H+][OH-] = 10-14

H2B = H+ + HB-

KA1 = [H+][HB-]/[H2B] = 10-pKa1

HB- = H+ + B2-

KA2 = [H+][B2-]/[HB-] = 10-pKa2

Mass Balance: BT = [H2B] + [HB-] +[B2-]= 10-3 M

NaT = [Na+] = BT

Charge Balance: 2[B2-] + [HB-] + [OH-] = [H+] + [Na+]

Proton Balance: [H2B] + [H+] = [B2-] + [OH-]

Diprotic Acid - NaHCO3 (salt of the

conjugate base of H2B)

What is the equilibrium pH for a

solution comprised of BT M of the salt
System: Closed
of the conjugate base of HB-?

Components: Na+, HB- & H2O

Species: H2B, HB-,B2- H2O, OH-, H+

Equilibria:
H2O = H+ + OH-

Kw = [H+][OH-] = 10-14

H2B = H+ + HB-

KA1 = [H+][HB-]/[H2B] = 10-pKa1

HB- = H+ + B2-

KA2 = [H+][B2-]/[HB-] = 10-pKa2

Mass Balance: BT = [H2B] + [HB-] +[B2-]= 10-3 M

NaT = [Na+] = 2BT

Charge Balance: 2[B2-] + [HB-] + [OH-] = [H+] + [Na+]

Proton Balance: 2[H2B] + [HB-] + [H+] = [OH-]

Diprotic Acid - NaHCO3 (salt of the

conjugate base of HB-)